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Preparation of Pure CO2 Standard Gas from Calcium Carbonate for Stable Isotope Analysis (탄산칼슘을 이용한 이산화탄소 안정동위원소 표준시료 제작에 대한 연구)

  • Park, Mi-Kyung;Park, Sunyoung;Kang, Dong-Jin;Li, Shanlan;Kim, Jae-Yeon;Jo, Chun Ok;Kim, Jooil;Kim, Kyung-Ryul
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.18 no.1
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    • pp.40-46
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    • 2013
  • The isotope ratios of $^{13}C/^{12}C$ and $^{18}O/^{16}O$ for a sample in a mass spectrometer are measured relative to those of a pure $CO_2$ reference gas (i.e., laboratory working standard). Thus, the calibration of a laboratory working standard gas to the international isotope scales (Pee Dee Belemnite (PDB) for ${\delta}^{13}C$ and Vienna Standard Mean Ocean Water (V-SMOW) for ${\delta}^{18}O$) is essential for comparisons between data sets obtained by other groups on other mass spectrometers. However, one often finds difficulties in getting well-calibrated standard gases, because of their production time and high price. Additional difficulty is that fractionation processes can occur inside the gas cylinder most likely due to pressure drop in long-term use. Therefore, studies on laboratory production of pure $CO_2$ isotope standard gas from stable solid calcium carbonate standard materials, have been performed. For this study, we propose a method to extract pure $CO_2$ gas without isotope fractionation from a solid calcium carbonate material. The method is similar to that suggested by Coplen et al., (1983), but is better optimized particularly to make a large amount of pure $CO_2$ gas from calcium carbonate material. The $CaCO_3$ releases $CO_2$ in reaction with 100% pure phosphoric acid at $25^{\circ}C$ in a custom designed, evacuated reaction vessel. Here we introduce optimal procedure, reaction conditions, and samples/reactants size for calcium carbonate-phosphoric acid reaction and also provide the details for extracting, purifying and collecting $CO_2$ gas out of the reaction vessel. The measurements for ${\delta}^{18}O$ and ${\delta}^{13}C$ of $CO_2$ were performed at Seoul National University using a stable isotope ratio mass spectrometer (VG Isotech, SIRA Series II) operated in dual-inlet mode. The entire analysis precisions for ${\delta}^{18}O$ and ${\delta}^{13}C$ were evaluated based on the standard deviations of multiple measurements on 15 separate samples of purified $CO_2$. The pure $CO_2$ samples were taken from 100-mg aliquots of a solid calcium carbonate (Solenhofen-ori $CaCO_3$) during 8-day experimental period. The multiple measurements yielded the $1{\sigma}$ precisions of ${\pm}0.01$‰ for ${\delta}^{13}C$ and ${\pm}0.05$‰ for ${\delta}^{18}O$, comparable to the internal instrumental precisions of SIRA. Therefore, we conclude the method proposed in this study can serve as a way to produce an accurate secondary and/or laboratory $CO_2$ standard gas. We hope this study helps resolve difficulties in placing a laboratory working standard onto the international isotope scales and does make accurate comparisons with other data sets from other groups.

Studies on the Derivation of the Instantaneous Unit Hydrograph for Small Watersheds of Main River Systems in Korea (한국주요빙계의 소유역에 대한 순간단위권 유도에 관한 연구 (I))

  • 이순혁
    • Magazine of the Korean Society of Agricultural Engineers
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    • v.19 no.1
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    • pp.4296-4311
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    • 1977
  • This study was conducted to derive an Instantaneous Unit Hydrograph for the accurate and reliable unitgraph which can be used to the estimation and control of flood for the development of agricultural water resources and rational design of hydraulic structures. Eight small watersheds were selected as studying basins from Han, Geum, Nakdong, Yeongsan and Inchon River systems which may be considered as a main river systems in Korea. The area of small watersheds are within the range of 85 to 470$\textrm{km}^2$. It is to derive an accurate Instantaneous Unit Hydrograph under the condition of having a short duration of heavy rain and uniform rainfall intensity with the basic and reliable data of rainfall records, pluviographs, records of river stages and of the main river systems mentioned above. Investigation was carried out for the relations between measurable unitgraph and watershed characteristics such as watershed area, A, river length L, and centroid distance of the watershed area, Lca. Especially, this study laid emphasis on the derivation and application of Instantaneous Unit Hydrograph (IUH) by applying Nash's conceptual model and by using an electronic computer. I U H by Nash's conceptual model and I U H by flood routing which can be applied to the ungaged small watersheds were derived and compared with each other to the observed unitgraph. 1 U H for each small watersheds can be solved by using an electronic computer. The results summarized for these studies are as follows; 1. Distribution of uniform rainfall intensity appears in the analysis for the temporal rainfall pattern of selected heavy rainfall event. 2. Mean value of recession constants, Kl, is 0.931 in all watersheds observed. 3. Time to peak discharge, Tp, occurs at the position of 0.02 Tb, base length of hlrdrograph with an indication of lower value than that in larger watersheds. 4. Peak discharge, Qp, in relation to the watershed area, A, and effective rainfall, R, is found to be {{{{ { Q}_{ p} = { 0.895} over { { A}^{0.145 } } }}}} AR having high significance of correlation coefficient, 0.927, between peak discharge, Qp, and effective rainfall, R. Design chart for the peak discharge (refer to Fig. 15) with watershed area and effective rainfall was established by the author. 5. The mean slopes of main streams within the range of 1.46 meters per kilometer to 13.6 meter per kilometer. These indicate higher slopes in the small watersheds than those in larger watersheds. Lengths of main streams are within the range of 9.4 kilometer to 41.75 kilometer, which can be regarded as a short distance. It is remarkable thing that the time of flood concentration was more rapid in the small watersheds than that in the other larger watersheds. 6. Length of main stream, L, in relation to the watershed area, A, is found to be L=2.044A0.48 having a high significance of correlation coefficient, 0.968. 7. Watershed lag, Lg, in hrs in relation to the watershed area, A, and length of main stream, L, was derived as Lg=3.228 A0.904 L-1.293 with a high significance. On the other hand, It was found that watershed lag, Lg, could also be expressed as {{{{Lg=0.247 { ( { LLca} over { SQRT { S} } )}^{ 0.604} }}}} in connection with the product of main stream length and the centroid length of the basin of the watershed area, LLca which could be expressed as a measure of the shape and the size of the watershed with the slopes except watershed area, A. But the latter showed a lower correlation than that of the former in the significance test. Therefore, it can be concluded that watershed lag, Lg, is more closely related with the such watersheds characteristics as watershed area and length of main stream in the small watersheds. Empirical formula for the peak discharge per unit area, qp, ㎥/sec/$\textrm{km}^2$, was derived as qp=10-0.389-0.0424Lg with a high significance, r=0.91. This indicates that the peak discharge per unit area of the unitgraph is in inverse proportion to the watershed lag time. 8. The base length of the unitgraph, Tb, in connection with the watershed lag, Lg, was extra.essed as {{{{ { T}_{ b} =1.14+0.564( { Lg} over {24 } )}}}} which has defined with a high significance. 9. For the derivation of IUH by applying linear conceptual model, the storage constant, K, with the length of main stream, L, and slopes, S, was adopted as {{{{K=0.1197( {L } over { SQRT {S } } )}}}} with a highly significant correlation coefficient, 0.90. Gamma function argument, N, derived with such watershed characteristics as watershed area, A, river length, L, centroid distance of the basin of the watershed area, Lca, and slopes, S, was found to be N=49.2 A1.481L-2.202 Lca-1.297 S-0.112 with a high significance having the F value, 4.83, through analysis of variance. 10. According to the linear conceptual model, Formular established in relation to the time distribution, Peak discharge and time to peak discharge for instantaneous Unit Hydrograph when unit effective rainfall of unitgraph and dimension of watershed area are applied as 10mm, and $\textrm{km}^2$ respectively are as follows; Time distribution of IUH {{{{u(0, t)= { 2.78A} over {K GAMMA (N) } { e}^{-t/k } { (t.K)}^{N-1 } }}}} (㎥/sec) Peak discharge of IUH {{{{ {u(0, t) }_{max } = { 2.78A} over {K GAMMA (N) } { e}^{-(N-1) } { (N-1)}^{N-1 } }}}} (㎥/sec) Time to peak discharge of IUH tp=(N-1)K (hrs) 11. Through mathematical analysis in the recession curve of Hydrograph, It was confirmed that empirical formula of Gamma function argument, N, had connection with recession constant, Kl, peak discharge, QP, and time to peak discharge, tp, as {{{{{ K'} over { { t}_{ p} } = { 1} over {N-1 } - { ln { t} over { { t}_{p } } } over {ln { Q} over { { Q}_{p } } } }}}} where {{{{K'= { 1} over { { lnK}_{1 } } }}}} 12. Linking the two, empirical formulars for storage constant, K, and Gamma function argument, N, into closer relations with each other, derivation of unit hydrograph for the ungaged small watersheds can be established by having formulars for the time distribution and peak discharge of IUH as follows. Time distribution of IUH u(0, t)=23.2 A L-1S1/2 F(N, K, t) (㎥/sec) where {{{{F(N, K, t)= { { e}^{-t/k } { (t/K)}^{N-1 } } over { GAMMA (N) } }}}} Peak discharge of IUH) u(0, t)max=23.2 A L-1S1/2 F(N) (㎥/sec) where {{{{F(N)= { { e}^{-(N-1) } { (N-1)}^{N-1 } } over { GAMMA (N) } }}}} 13. The base length of the Time-Area Diagram for the IUH was given by {{{{C=0.778 { ( { LLca} over { SQRT { S} } )}^{0.423 } }}}} with correlation coefficient, 0.85, which has an indication of the relations to the length of main stream, L, centroid distance of the basin of the watershed area, Lca, and slopes, S. 14. Relative errors in the peak discharge of the IUH by using linear conceptual model and IUH by routing showed to be 2.5 and 16.9 percent respectively to the peak of observed unitgraph. Therefore, it confirmed that the accuracy of IUH using linear conceptual model was approaching more closely to the observed unitgraph than that of the flood routing in the small watersheds.

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Radiation Therapy and Chemotherapy after Breast Conserving Surgery for Invasive Breast Cancer: An Intermediate Result (침윤성 유방암에서 유방보존수술 후 방사선치료 및 항암화학 병용치료의 성적 및 위험인자 분석)

  • Lee, Seok-Ho;Choi, Jin-Ho;Lee, Young-Don;Park, Heoung-Kyu;Kim, Hyun-Young;Park, Se-Hoon;Lee, Kyu-Chan
    • Radiation Oncology Journal
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    • v.25 no.1
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    • pp.16-25
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    • 2007
  • [ $\underline{Purpose}$ ]: Breast conserving surgery (BCS) followed by chemotherapy (CTx.) and radiation therapy (RT) is widely performed for the treatment of early breast cancer. This retrospective study was undertaken to evaluate our interim results in terms of failure patterns, survival and relative risk factors. $\underline{Materials\;and\;Methods}$: From January 1999 through December 2003, 129 patients diagnosed with invasive breast cancer and treated with BCS followed by RT were subject to retrospective review. The median age of the patients was 45 years (age distribution, $27{\sim}76$ years). The proportions of patients according to their tumor, nodes, and metastases (TNM) stage were 65 (50.4%) in stage I, 41 (31.7%) in stage IIa, 13 (10.1%) in stage IIb, 9 (7.0%) in stage III, and 1 patient (0.8%) in stage IIIc. For 32 patients (24.8%), axillary node metastasis was found after dissection. BCS consisted of quadrantectomy in 115 patients (89.1%) and lumpectomy in 14 patients (10.6%). Axillary node dissection at axillary level I and II was performed for 120 patients (93%). For 7 patients (5.4%), only sentinel node dissection was performed with BCS. For 2 patients (1.6%) axillary dissection of any type was not performed. Postoperative RT was given with 6 MV X-rays. A tumor dose of 50.4 Gy was delivered to the entire breast area using a tangential field with a wedge compensator. An aditional dose of $9{\sim}16\;Gy$ was given to the primary tumor bed areas with electron beams. In 30 patients (23.3%), RT was delivered to the supraclavicular node. Most patients had adjuvant CTx. with $4{\sim}6$ cycles of CMF (cyclophosphamide, methotrexate, 5-fluorouracil) regimens. The median follow-up period was 50 months (range: $17{\sim}93$ months). $\underline{Results}$: The actuarial 5 year survival rate (5Y-OSR) was 96.9%, and the 5 year disease free survival rate (5Y-DFSR) was 93.7%. Local recurrences were noted in 2 patients (true: 2, regional node: 1) as the first sign of recurrence at a mean time of 29.3 months after surgery. Five patients developed distant metastases as the first sign of recurrence at $6{\sim}33$ months (mean 21 months). Sites of distant metastatic sites were bone in 3 patients, liver in 1 patient and systemic lesions in 1 patient. Among the patients with distant metastatic sites, two patients died at 17 and 25 months during the follow-up period. According to stage, the 5Y-OSR was 95.5%, 100%, 84.6%, and 100% for stage I, IIa, IIb, and III respectively. The 5Y-DFSR was 96.8%, 92.7%, 76.9%, and 100% for stage I, IIa, IIb, and III respectively. Stage was the only risk factor for local recurrence based on univariate analysis. Ten stage III patients included in this analysis had a primary tumor size of less than 3 cm and had more than 4 axillary lymph node metastases. The 10 stage III patients received not only breast RT but also received posterior axillary boost RT to the supraclavicular node. During the median 53.3 months follow-up period, no any local or distant failure was found. Complications were asymptomatic radiation pneumonitis in 10 patients, symptomatic pneumonitis in 1 patient and lymphedema in 8 patients. $\underline{Conclusion}$: Although our follow up period is short, we had excellent local control and survival results and reaffirmed that BCS followed by RT and CTx. appears to be an adequate treatment method. These results also provide evidence that distant failure occurs earlier and more frequent as compared with local failure. Further studies and a longer follow-up period are needed to assess the effectiveness of BCS followed by RT for the patients with less than a 3 cm primary tumor and more than 4 axillary node metastases.

Analysis of Greenhouse Thermal Environment by Model Simulation (시뮬레이션 모형에 의한 온실의 열환경 분석)

  • 서원명;윤용철
    • Journal of Bio-Environment Control
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    • v.5 no.2
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    • pp.215-235
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    • 1996
  • The thermal analysis by mathematical model simulation makes it possible to reasonably predict heating and/or cooling requirements of certain greenhouses located under various geographical and climatic environment. It is another advantages of model simulation technique to be able to make it possible to select appropriate heating system, to set up energy utilization strategy, to schedule seasonal crop pattern, as well as to determine new greenhouse ranges. In this study, the control pattern for greenhouse microclimate is categorized as cooling and heating. Dynamic model was adopted to simulate heating requirements and/or energy conservation effectiveness such as energy saving by night-time thermal curtain, estimation of Heating Degree-Hours(HDH), long time prediction of greenhouse thermal behavior, etc. On the other hand, the cooling effects of ventilation, shading, and pad ||||&|||| fan system were partly analyzed by static model. By the experimental work with small size model greenhouse of 1.2m$\times$2.4m, it was found that cooling the greenhouse by spraying cold water directly on greenhouse cover surface or by recirculating cold water through heat exchangers would be effective in greenhouse summer cooling. The mathematical model developed for greenhouse model simulation is highly applicable because it can reflects various climatic factors like temperature, humidity, beam and diffuse solar radiation, wind velocity, etc. This model was closely verified by various weather data obtained through long period greenhouse experiment. Most of the materials relating with greenhouse heating or cooling components were obtained from model greenhouse simulated mathematically by using typical year(1987) data of Jinju Gyeongnam. But some of the materials relating with greenhouse cooling was obtained by performing model experiments which include analyzing cooling effect of water sprayed directly on greenhouse roof surface. The results are summarized as follows : 1. The heating requirements of model greenhouse were highly related with the minimum temperature set for given greenhouse. The setting temperature at night-time is much more influential on heating energy requirement than that at day-time. Therefore It is highly recommended that night- time setting temperature should be carefully determined and controlled. 2. The HDH data obtained by conventional method were estimated on the basis of considerably long term average weather temperature together with the standard base temperature(usually 18.3$^{\circ}C$). This kind of data can merely be used as a relative comparison criteria about heating load, but is not applicable in the calculation of greenhouse heating requirements because of the limited consideration of climatic factors and inappropriate base temperature. By comparing the HDM data with the results of simulation, it is found that the heating system design by HDH data will probably overshoot the actual heating requirement. 3. The energy saving effect of night-time thermal curtain as well as estimated heating requirement is found to be sensitively related with weather condition: Thermal curtain adopted for simulation showed high effectiveness in energy saving which amounts to more than 50% of annual heating requirement. 4. The ventilation performances doting warm seasons are mainly influenced by air exchange rate even though there are some variations depending on greenhouse structural difference, weather and cropping conditions. For air exchanges above 1 volume per minute, the reduction rate of temperature rise on both types of considered greenhouse becomes modest with the additional increase of ventilation capacity. Therefore the desirable ventilation capacity is assumed to be 1 air change per minute, which is the recommended ventilation rate in common greenhouse. 5. In glass covered greenhouse with full production, under clear weather of 50% RH, and continuous 1 air change per minute, the temperature drop in 50% shaded greenhouse and pad & fan systemed greenhouse is 2.6$^{\circ}C$ and.6.1$^{\circ}C$ respectively. The temperature in control greenhouse under continuous air change at this time was 36.6$^{\circ}C$ which was 5.3$^{\circ}C$ above ambient temperature. As a result the greenhouse temperature can be maintained 3$^{\circ}C$ below ambient temperature. But when RH is 80%, it was impossible to drop greenhouse temperature below ambient temperature because possible temperature reduction by pad ||||&|||| fan system at this time is not more than 2.4$^{\circ}C$. 6. During 3 months of hot summer season if the greenhouse is assumed to be cooled only when greenhouse temperature rise above 27$^{\circ}C$, the relationship between RH of ambient air and greenhouse temperature drop($\Delta$T) was formulated as follows : $\Delta$T= -0.077RH+7.7 7. Time dependent cooling effects performed by operation of each or combination of ventilation, 50% shading, pad & fan of 80% efficiency, were continuously predicted for one typical summer day long. When the greenhouse was cooled only by 1 air change per minute, greenhouse air temperature was 5$^{\circ}C$ above outdoor temperature. Either method alone can not drop greenhouse air temperature below outdoor temperature even under the fully cropped situations. But when both systems were operated together, greenhouse air temperature can be controlled to about 2.0-2.3$^{\circ}C$ below ambient temperature. 8. When the cool water of 6.5-8.5$^{\circ}C$ was sprayed on greenhouse roof surface with the water flow rate of 1.3 liter/min per unit greenhouse floor area, greenhouse air temperature could be dropped down to 16.5-18.$0^{\circ}C$, whlch is about 1$0^{\circ}C$ below the ambient temperature of 26.5-28.$0^{\circ}C$ at that time. The most important thing in cooling greenhouse air effectively with water spray may be obtaining plenty of cool water source like ground water itself or cold water produced by heat-pump. Future work is focused on not only analyzing the feasibility of heat pump operation but also finding the relationships between greenhouse air temperature(T$_{g}$ ), spraying water temperature(T$_{w}$ ), water flow rate(Q), and ambient temperature(T$_{o}$).

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